JP5653646B2 - Method for producing granulated product containing nucleated enzyme - Google Patents

Description

  The present invention relates to a method for producing a nucleated enzyme-containing granulated product.

  In many cases, various detergents and bleaching agents for clothing are blended with various enzymes in order to enhance their detergency. This enzyme dissolves in water during use and exerts its effect. Therefore, it is important to keep the function without inactivating the enzyme, for example, by minimizing the contact between the enzyme and the detergent component or outside air during the period from the production to the use. Moreover, the form of the granulated material is preferable to the fine powder from the viewpoint of handling by workers during manufacture and consumers during use. Therefore, an enzyme is usually blended as a granulated product when blended with a cleaning agent or the like.

  As a method for producing a nucleated enzyme-containing granulated product, a method of dry granulating enzyme powder together with a water-soluble core substance and a water-soluble organic binder by a stirring tumbling granulator is mainly used (Patent Document 1). . In order to continuously produce an enzyme-containing granulated product, first, only the water-soluble nuclear material is charged, the stirring tumbling granulator is heated to a specific temperature while stirring, and then other raw materials are charged. , Continuous manufacturing method of enzyme granules for detergent (Patent Document 2), and the step of drying enzyme solution to form enzyme enzyme preparation and / or powdered form to suppress enzyme deactivation A method for producing an enzyme-containing granulated product (Patent Document 3) or the like in which the step of granulating an enzyme preparation is performed in the presence of an amino acid (salt) has been proposed.

Japanese Patent Laid-Open No. 62-257990 JP 2007-70556 A JP 2008-164489 A

However, in the dry granulation method using a stirring tumbling granulator, there is a problem in that a granule having a particle size other than the nucleated enzyme-containing granule having a desired particle size is simultaneously produced, resulting in a low yield. . Moreover, in order for the nucleated enzyme-containing granulated product to exhibit the performance as a cleaning agent, it is desired that the enzyme activity is high.
Therefore, the subject of this invention is providing the method which can manufacture a highly active nucleated enzyme containing granulated material with sufficient yield.

  As a result of the study by the present inventors, in the production of a nucleated enzyme-containing granulated product using a stirring tumbling granulator, a granulated product other than the desired particle size generated in the granulation step is extracted from the nucleated enzyme-containing granulated product. After separation and pulverization, it was found that a nucleated enzyme-containing granulated product can be obtained with high yield by recycling a component having a specific particle size distribution as a granulation raw material. In addition, there is concern about whether the enzyme activity remains after the recovered pulverization because the component to be reused has undergone the pulverization step. However, it was found that by using a component having a specific particle size distribution, a nucleated enzyme-containing granule having an improved enzyme activity was unexpectedly obtained.

That is, the present invention is a method for producing a nucleated enzyme-containing granulated product using a raw material containing a core substance and an enzyme and using a stirring tumbling granulator, which comprises the following steps (1) to (1): (4),
(1) a step of separating a granulated product other than the desired particle size from the nucleated enzyme-containing granulated product,
(2) A step of obtaining a pulverized product by pulverizing a granulated product other than the desired desired particle size,
(3) A component having an average particle size of 0.06 to 0.5 times the average particle size of the desired nucleated enzyme-containing granulated product is separated from the pulverized product, and recovered enzyme Obtaining as a powder,
(4) A step of producing a nucleated enzyme-containing granulated product using a stirring tumbling granulator using a raw material containing a core substance, an enzyme, and a recovered enzyme powder,
The manufacturing method of the nucleated enzyme containing granulated material which has this is provided.

  According to the present invention, a highly active nucleated enzyme-containing granulated product can be obtained with good yield. In addition, consumption of raw materials can be reduced.

  The nucleated enzyme-containing granulated product in the present invention is a nucleated granulated product that is granulated with the enzyme attached to the surface of the substance that becomes the nucleus.

  The average particle diameter of the substance serving as the nucleus is preferably 200 μm or more in view of the nucleus forming ability. The average particle size is preferably 200 to 850 μm, more preferably 350 to 800 μm, and particularly preferably 425 to 700 μm from the viewpoint of granulation yield. Further, particles having a particle size of 420 μm or less are preferably 10% or less, more preferably 7% or less, particularly preferably 5% or less, and particles having a particle size of 710 μm or more are preferably 10% or less, more preferably 7% or less, particularly 5%. The following is preferable from the same point.

  From the viewpoint of the yield of the nucleated enzyme-containing granule to be obtained, the amount of the core substance to be charged is preferably 30 to 80% by mass (hereinafter simply referred to as “%”) of the entire nucleated enzyme-containing granule. Furthermore, 40 to 60% is preferable.

Since the core substance is preferably highly soluble when used as a cleaning agent or a bleaching agent, it is preferably water-soluble (hereinafter also referred to as a water-soluble core substance).
Here, examples of the water-soluble nuclear material include sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, sugar and the like.

  The enzyme in the present invention is not particularly limited as long as it is an enzyme that exhibits an effect when mixed in a detergent, and examples thereof include protease, esterase, carbohydrase and the like. Specific examples of protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, papain, aminopeptidase, carboxypeptidase and the like. Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like. Specific examples of carbohydrase include cellulase, maltase, saccharase, amylase, pectinase, α- and β-glycosidase. These can use 1 type (s) or 2 or more types. Among them, it is preferable to use a proteolytic enzyme, that is, a protease.

  The enzyme is preferably used in the form of enzyme powder. The enzyme powder can be obtained by drying a solution containing the enzyme by a conventional method such as spray drying. In the solution containing the enzyme, a diluent for keeping the enzyme activity constant can be blended as necessary. Examples of the diluent include sulfates, halides, carbonates, phosphates, silicates, boric acid or salts thereof, saccharides, and the like.

  The content of the enzyme powder in the nucleated enzyme-containing granulated product is not particularly limited, but is generally preferably 0.01 to 30%, more preferably 0 in view of the effect when blended with a detergent. .1-30%.

  In the case of attaching an enzyme to the surface of a substance serving as a nucleus, it is preferable to use a water-soluble binder from the viewpoint of solubility. As a water-soluble binder, a water-soluble organic binder having a melting point or a softening point of 25 to 90 ° C. suppresses caking of the granulated product during storage, solubility of the granulated product, and suppression of enzyme deactivation during granulation. To preferred. The melting point or softening point is preferably 30 to 80 ° C., more preferably 35 to 70 ° C. from the same point. Specific examples of the substance include (a) polyethylene glycol or a derivative thereof, a water-soluble polymer selected from the group consisting of polyoxyethylene-polyoxypropylene glycol copolymers, and (b) nonionics such as polyoxyethylene alkyl ether. Surfactants, (c) polycarboxylic acid salts having an average molecular weight of 4000 or more, and the like, and one or a mixture of these can be used. Among these, polyethylene glycol is preferable from the viewpoint of solubility of the enzyme-containing granulated product.

  The amount of water-soluble binder used cannot be generally described because there are differences in the properties of each binder. Generally preferred. Therefore, the content of the water-soluble binder is preferably 5 to 50%, more preferably 10 to 30% in the nucleated enzyme-containing granulated product.

The nucleated enzyme-containing granulated product may further contain a powdery extender; a surfactant; an organic substance such as sugar or carboxymethyl cellulose, a dye, a dye, or a pigment, if necessary.
For example, it is preferable to use one or more inorganic salts selected from the group consisting of sulfates, carbonates, and hydrochlorides of alkali metals or alkaline earth metals as the powdery extender. Of these, water-soluble inorganic alkali metal salts such as sodium sulfate, sodium carbonate, and sodium chloride are preferred because they do not affect the cleaning performance. Other extenders include water-soluble organic acid salts such as sodium citrate, talc, titanium oxide, calcium carbonate, zeolite, magnesium carbonate, activated clay, kaolin, diatomaceous earth, bentonite, perlite, and acid clay.

  The nucleated enzyme-containing granulated product in the present invention is produced using a stirring tumbling granulator. Here, the stirring tumbling granulator generally has a main stirring shaft provided with stirring blades in the center, and further has an auxiliary stirring shaft for further assisting mixing and suppressing the generation of coarse particles. This is a granulator having a structure protruding from the wall surface in a direction perpendicular to the main stirring shaft. As the stirring tumbling granulator, Henschel mixer (Mitsui Miike Chemical Co., Ltd.), high speed mixer (Fukae Powtech Co., Ltd.), and the main stirring shaft are installed perpendicular to the bottom. Earth Technica), vertical granulator (Fuji Sangyo Co., Ltd.) and the like. Examples of those in which the main stirring shaft is installed horizontally include a Redige mixer (Matsuzaka Giken Co., Ltd.) and a pro shear mixer (Pacific Kiko Co., Ltd.).

  The granulation is preferably dry granulation. Dry granulation means a granulation method that does not use water as a binder, and the water content in the binder during granulation is 0 to 10%, more preferably 0 to 5%, especially 0 to 3%. This is preferable from the viewpoint of inhibiting enzyme deactivation during granulation.

  The temperature at the time of granulation is preferably near the melting point or softening point of the water-soluble binder. 40 to 110 ° C., further 45 to 100 ° C., particularly 50 to 90 ° C. is the point of operativity and inhibition of enzyme deactivation during granulation. To preferred.

  A granulated product containing a nucleated enzyme is obtained by granulation. The desired particle size can be appropriately determined depending on the intended use. In the present invention, the desired particle size of the nucleated enzyme-containing granulated product has an average particle size of 350 to 1000 μm, more preferably in the range of 400 to 700 μm. In view of granulation yield, solubility in water, and bulk density, those are preferred. Moreover, it is preferable from the same point that the particle diameter range of the desired nucleated enzyme-containing granulated product is in the range of 212 to 2800 μm, and more preferably 355 to 1000 μm.

During granulation, granules other than the desired particle size of the present invention, that is, coarse particles having a particle size larger than the desired particle size, and fine powder having a particle size smaller than the desired particle size are simultaneously generated. In this invention, it has the process (1) which isolate | separates the granulated material other than a desired particle size from a nucleated enzyme containing granulated material.
The coarse particles and fine powder are preferably separated by sieving. Specifically, a desired nucleated enzyme-containing granulated product is obtained using a sieve according to the purpose, and coarse particles and fine powder removed after sieving are collected. As the sieve, it is preferable to use a metal mesh sieve according to JIS Z 8801.

  Moreover, in this invention, it has the process (2) which grind | pulverizes the granulated material other than the desired particle size isolate | separated in process (1), and obtains a ground material. The pulverization method is not particularly limited, and can be performed by, for example, a method using a pulverizer such as a turbo mill or a blade mill. The pulverization conditions such as the pulverization time, the temperature during pulverization, and the rotational speed of the pulverizer may be set as appropriate in order to form desired particles. For example, when a turbo mill is used, it is performed at 1000 to 5000 r / min. It is preferable to carry out at 2000 to 3000 r / min. The pulverization temperature is preferably less than the melting point or softening point of the water-soluble binder used. The pulverized product after pulverization may be a product obtained by mixing coarse particles and fine powder, and may be obtained by mixing fine particles with a product obtained by pulverizing coarse particles.

  In the present invention, from the pulverized product obtained in step (2), the average particle size is in the range of 0.06 to 0.5 times the average particle size of the desired nucleated enzyme-containing granulated product. There is a step (3) of separating the components and obtaining the recovered enzyme powder. This ratio is preferably 0.1 to 0.5 times, more preferably 0.15 to 0.4 times, and particularly preferably 0.2 to 0.3 times in terms of granulation properties and enzyme deactivation. The desired component can be obtained, for example, by appropriately adjusting the conditions during pulverization and further classifying with a sieve as described above.

The average particle size of the recovered enzyme powder is preferably 40 to 300 μm, more preferably 75 to 230 μm, and particularly preferably 100 to 150 μm from the viewpoint of enhancing enzyme activity and granulating properties. In addition, in this specification, an average particle diameter means the average value calculated | required according to a volume reference | standard by the laser diffraction scattering method.
Further, the particle diameter range of the recovered enzyme powder is preferably 32 to 355 μm, more preferably 75 to 180 μm, and particularly preferably 100 to 150 μm from the same point. In the present specification, the particle size range means the width of the JIS standard sieve opening.

In the present invention, the recovered enzyme powder is used as a part of the raw material. That is, this invention has the process (4) which manufactures a nucleated enzyme containing granulated material using the raw material containing the substance used as a core, an enzyme, and the collect | recovered enzyme powder using a stirring rolling granulator.
The content of the recovered enzyme powder in the raw material in the step (4) is preferably 3 to 25%, more preferably 4 to 20%, particularly 5 to 15%, particularly 6 to 12% from the viewpoint of granulation.

  The above process may be repeated multiple times. That is, a nucleated enzyme-containing granulated product is produced using the recovered enzyme powder, and further, a granulated product having a particle size other than the desired particle size is separated from the nucleated enzyme-containing granulated product, and the granulated product is pulverized and pulverized. From the pulverized product, the component having an average particle size of 0.06 to 0.5 times the average particle size of the desired nucleated enzyme-containing granulated product is separated and recovered enzyme powder A nucleated enzyme-containing granulated product can be produced using a stirring tumbling granulator using a raw material containing a core substance, an enzyme, and the recovered enzyme powder.

  The nucleated enzyme-containing granulated product of the present invention can be coated as necessary. Although it does not restrict | limit especially as a coating agent, Water-soluble film forming polymers, such as polyethyleneglycol, polyacrylate, polyvinyl alcohol, polyvinylpyrrolidone, a cellulose derivative, a starch derivative; These polymers, talc, clay, titanium oxide, calcium carbonate And water-soluble or sparingly soluble inorganic particles, or a combination with a protective agent such as alkali metal silicate and alkali metal carbonate. The coating agent may be 0.01 to 0.7 parts, more preferably 0.05 to 0.6 parts, based on 100 parts by mass of the nucleated enzyme-containing granulated product (hereinafter simply referred to as “parts”). From the viewpoint of the effect of improving the storage stability.

  Examples of the coating method include a method of coating by a conventional method using an apparatus such as a fluidized bed granulator, a coating pan granulator, and a stirring granulator.

  The nucleated enzyme-containing granulated product produced by the method of the present invention is useful as a blending component of a detergent composition, and the detergent composition blended with this is a detergent for clothing, tableware, dwelling, etc. Can be used as

[Analysis method]
<Measurement of average particle size>
LS 13 320 (manufactured by BECKMAN COULTER) was used for measurement by laser diffraction scattering method.

<Yield calculation method>
The yield of the nucleated enzyme-containing granulated product was calculated by the following formula.
Desired nucleated enzyme-containing granulated material weight / input material weight × 100 (%)

<Method for measuring enzyme activity>
100 mM AAPL (Protein Laboratory: Glt-Ala-Ala-Pro-Leu-pNA dissolved in dimethyl sulfoxide: used as final concentration 5 mM) and phosphate buffer (1/15 mol / L, pH 7.4) to 0.9 ml 0.05 ml of the enzyme solution was added and reacted at 30 ° C. for 10 minutes. The reaction was stopped by adding 2 ml of a 5% (w / v) citric acid solution, and the absorbance at 420 nm was measured using a spectrophotometer. The value obtained by multiplying the obtained value by the dilution rate of the enzyme was used as the protease titer.

<Calculation method of activity yield>
The activity yield was calculated by the following formula.
Nucleated enzyme-containing granulated product actual activity / nucleated enzyme-containing granulated product theoretical activity x 100 (%)
Here, the theoretical activity of the nucleated enzyme-containing granulated product is the activity of the enzyme powder before granulation [U / g-enzyme powder] and the content of enzyme powder in the granulated product [g-enzyme powder / g- Is the enzyme activity per unit weight of the granulated product [U / g-granulated product].
In addition, when the recovered enzyme powder is used, the enzyme powder content [G / enzyme powder] and the recovered enzyme powder activity [U / g-enzyme powder] in the granulated product [ [g-enzyme powder / g-granulated product] multiplied by the recovered enzyme powder content [g-enzyme powder / g-granulated product] and added.
The nucleated enzyme-containing granulated product actual activity is the enzyme activity [U / g-granulated product] per unit weight of the granulated product obtained by granulation.

[Preparation of enzyme powder]
Bacillus sp. KSM-9865 (FEM-P18566) derived protease (enzyme solid content 6%) solution (quaternary ammonium salt (Cotamine 60W, Kao Co., Ltd.) 0.1 parts per 100 parts enzyme solids) in sulfuric acid Sodium was added and dried with a co-current spray dryer to obtain enzyme powder.

〔material〕
Baked salt (5% or less of particles having a particle size of 710 μm or more, 5% or less of particles having a particle size of 420 μm or less, and an average particle size of 520 μm) was used as a core substance.
Polyethylene glycol (PEG6000 (Kao Corporation), melting point 60 ° C.) was used as a binder.
As the sodium sulfate, a powder having an average particle size of 100 μm or less was used.
Comparative Example 1
[First granulation]
Enzyme powder (100 parts), sodium sulfate (163 parts), polyethylene glycol (35 parts), baked salt (586 parts), and titanium oxide (75 parts) were used as raw materials.
The raw material is put into a high speed mixer (manufactured by Earth Technica Co., Ltd.), and while stirring hot water at 90 ° C, the agitator 540r / min and chopper 900r / min are stirred and rolled, and the contents are raised to 88 ° C. I let you. Thereafter, the hot water was stopped, cooling water was poured into the jacket, and the contents were cooled to 54 ° C. A granulated product was obtained by a granulating operation for about 1 hour and 15 minutes after the raw material was charged. By sieving this granulated product with a sieve (1000 μm · 355 μm), 895 parts of desired nucleated enzyme-containing granulated product (particle size range 1000 μm to 355 μm, average particle size 570 μm, the same applies hereinafter) and oversize (particle size) A granulated product having 96 parts in the range (over 1000 μm) and 75 parts in undersize (particle size range less than 355 μm) was obtained. The yield, activity yield, and product of the desired nucleated enzyme-containing granulated product are shown in Table 1 (the same applies hereinafter).

Comparative Example 2
The oversize obtained in the first granulation was pulverized for 1 Pass with a turbo mill (2000 r / min), then mixed with the undersize, and sieved with a sieve (180 μm / 425 μm) to obtain a particle size range of 180 to 425 μm and an average particle size A recovered enzyme powder of 320 μm was obtained. This recovered enzyme powder (107 parts), enzyme powder (100 parts), sodium sulfate (163 parts), polyethylene glycol (35 parts), grilled salt (586 parts), and titanium oxide (75 parts) were mixed with a high speed mixer (Earth Technica). And a granulation operation was performed under the same conditions as in Comparative Example 1 to obtain a nucleated enzyme-containing granulated product.

Example 1
An oversize obtained by the first granulation and an undersize obtained by pulverizing 1 Pass by a turbo mill (2500 r / min) are used as a pulverized product, and a particle size range of 100 to 180 μm is obtained by sieving with a sieve (100 μm / 180 μm) A recovered enzyme powder having an average particle size of 150 μm was obtained. Using this recovered enzyme powder (107 parts), enzyme powder (100 parts), sodium sulfate (163 parts), polyethylene glycol (35 parts), baked salt (586 parts), and titanium oxide (75 parts), Similarly, stirring and rolling granulation was performed to obtain a desired nucleated enzyme-containing granulated product.

Example 2
The pulverized product obtained in Example 1 was sieved with a sieve (100 μm · 150 μm) to obtain a recovered enzyme powder having a particle size range of 100 to 150 μm and an average particle size of 120 μm. Using this recovered enzyme powder (107 parts), enzyme powder (100 parts), sodium sulfate (163 parts), polyethylene glycol (35 parts), baked salt (586 parts), and titanium oxide (75 parts) Similarly, stirring and rolling granulation was performed to obtain a desired nucleated enzyme-containing granulated product.

Example 3
The pulverized product obtained in Example 1 was sieved with a sieve (75 μm · 149 μm) to obtain a recovered enzyme powder having a particle size range of 75 to 149 μm and an average particle size of 100 μm. Using this recovered enzyme powder (107 parts), enzyme powder (100 parts), sodium sulfate (163 parts), polyethylene glycol (35 parts), baked salt (586 parts), and titanium oxide (75 parts) Similarly, stirring and rolling granulation was performed to obtain a desired nucleated enzyme-containing granulated product.

Example 4
The oversize and undersize obtained in the first granulation are pulverized for 1 pass with a turbo mill (4000 r / min), and sieved with a sieve (32 μm / 75 μm) to obtain a particle size range of 32 to 75 μm and an average particle size of 50 μm. The recovered enzyme powder was obtained. Using this recovered enzyme powder (107 parts), enzyme powder (100 parts), sodium sulfate (163 parts), polyethylene glycol (35 parts), baked salt (586 parts), and titanium oxide (75 parts) Similarly, stirring and rolling granulation was performed to obtain a desired nucleated enzyme-containing granulated product.

  As shown in Table 1, after recovering and pulverizing a granulated product other than the nucleated enzyme-containing granulated product having a desired particle size generated in the granulation step, a specific particle size distribution component is used as the next granulating raw material. By recycling, a nucleated enzyme-containing granulated product with high yield and high activity was obtained. In particular, a highly active nucleated enzyme-containing granulated product was obtained with good yield by setting the average particle size after pulverization to 100 to 150 μm.

Claims (7)

A method for producing a nucleated enzyme-containing granulated product using a stirring tumbling granulator using a raw material containing a core substance and an enzyme, comprising the following steps (1) to (4):
(1) a step of separating a granulated product other than the desired particle size from the nucleated enzyme-containing granulated product,
(2) A step of obtaining a pulverized product by pulverizing a granulated product other than the desired desired particle size,
(3) A component having an average particle size of 0.06 to 0.5 times the average particle size of the desired nucleated enzyme-containing granulated product is separated from the pulverized product, and recovered enzyme Obtaining as a powder,
(4) A step of producing a nucleated enzyme-containing granulated product using a stirring tumbling granulator using a raw material containing a core substance, an enzyme, and a recovered enzyme powder,
A method for producing a nucleated enzyme-containing granulated product.   The manufacturing method of the nucleated enzyme containing granulated material of Claim 1 whose content of the collect | recovered enzyme powder in the raw material in a process (4) is 3-25 mass%. The manufacturing method of the nucleated enzyme containing granulated material of Claim 1 or 2 whose average particle diameter of the nucleated enzyme containing granulated material of a desired particle size is 350-1000 micrometers.   The manufacturing method of the nucleated enzyme containing granulated material of any one of Claims 1-3 whose average particle diameter of the substance used as a nucleus is 200-850 micrometers.   The method for producing a nucleated enzyme-containing granulated product according to any one of claims 1 to 4, wherein the average particle size of the recovered enzyme powder is 40 to 300 µm.   The manufacturing method of the nucleated enzyme containing granulated material of any one of Claims 1-5 whose substance used as a nucleus is water-soluble.   The manufacturing method of the nucleated enzyme containing granulated material of any one of Claims 1-6 whose substance used as a nucleus is sodium chloride.